Introduction: The aim of this study was to explore the specific vocational identity of secondary school students whose first choice of degree program is Psychology. In particular, this study analyzes when their interest in Psychology began, the curriculum track taken in high school and their profile of vocational interests and values. Method: The sample was made up of 4715 subjects in their final year of secondary education at public or private schools in the Greater Madrid region (Spain); 43.9% were male, and the mean age was 17.38 years (SD = 0.64). Subjects completed the Project Orion battery of guidance questionnaires. A subsample of 509 students wished to study Psychology; their mean age was 17.38 years (SD = 0.69), and 76.2% were female. Results: The results showed significant differences in the profile of vocational interests and values of students who wished to study Psychology, in comparison to the others. Specifically, students opting for Psychology showed greater interest in the area of Healthcare, followed by interests in the vocational area of Teaching and Guidance. Furthermore, the vocational values that characterize students who wish to study Psychology were: "Helping people," "Doing something useful and important" and "Pursuing higher values." The guidance they had received from teachers and school counselors about which curriculum track to follow in upper secondary school was appropriate.